Inorganic Chemistry最新文献

The rapid and accurate detection of antibiotics and diseasebiomarkersis crucial for disease prevention, diagnosis, and treatment. Herein,a novel multidentate ligand containing a benzothiadiazole unit, namely,4,7-bis(1H-imidazol-1-yl)benzo-[2,1,3]thiadiazole(BIBT), together with 4,4′-stilbenedicaroxylic acid (H₂SBCA), was employed to synthesize a new three-dimensionalseven-fold interpenetrating stable Zn^II metal–organicframework (MOF) under solvothermal conditions, with the chemical formula{[Zn₄(BIBT)₄(SBCA)₄]·DMF}_n (JXUST-67, where JXUST refers toJiangxi University of Science and Technology; DMF = N,N-dimethylformamide). After immersion in aqueoussolutions at pH 2–12 for 24 h, JXUST-67 remainedstructurally intact. Fluorescence sensing experiments demonstratethat JXUST-67 can serve as a fast-response (≤10s) turn-off sensor for nitrofurazone (NFZ) and a turn-on sensor for2,6-pyridinedicarboxylic acid (DPA) and both analytes can be recognizedby the naked eye, achieving detection limits of 0.1378 and 0.0048μM, respectively. Furthermore, cycling tests show that JXUST-67 is a reusable sensor material. More importantly, JXUST-67 exhibits good biocompatibility and low cytotoxicitytoward living cells and successfully detects DPA in live cells, demonstratingsignificant potential for biosensing applications.

Thisstudy evaluates CuFeO₂ and CuFe₂O₄ as promising catalysts for photothermal CO₂ conversionand their ability to form plasmonic Cu nanoparticles in situ. A straightforward,reproducible, aqueous citrate-based solution-gel method with highstoichiometric control was developed to synthesize both catalystsfrom the same starting materials. XRD, Raman, and ICP-OES confirmednearly phase-pure materials with appropriate bandgaps (1.13 eV forCuFeO₂ and 1.55 eV for CuFe₂O₄),determined by UV–vis spectroscopy. SEM and BET analyses showeda dense morphology for CuFeO₂ and a slightly more porousCuFe₂O₄ architecture. The catalysts were testedin a photoreactor, where they selectively form CO via the reversewater–gas shift reaction. The combination of light and heatcauses exsolution of copper onto the surface. These nanoparticlesexhibit the localized surface plasmon resonance effect (LSPR), whichfacilitates CO₂ conversion. The CuFeO₂ catalystproduces 62 mmol of CO g_catalyst^–1 h^–1, and CuFe₂O₄ produces 65 mmolof CO g_catalyst^–1 h^–1, both using a combination of reactor heating and catalyst illumination.The key advancements are the development of a universal aqueous solution-gelroute to structurally distinct copper iron oxides and the identificationof an in situ Cu exsolution mechanism that converts these materialsfrom pre-catalysts into active photothermal catalysts.

Theintegration of chirality and magnetism into discrete metal–organicarchitectures remains a formidable synthetic challenge, particularlywhen both the cage framework and the encapsulated complex are chiraland paramagnetic. This challenge lies in controlling the stereochemistryof both components while establishing pathways for magnetic exchangebetween their paramagnetic metal centers within a discrete host–guestassembly. In this paper, we report a new series of enantiopure paramagnetictrigonal bipyramidal Co^II₅L₆ cageframeworks, which are templated by twin carbonate ions or a chiral-at-metalmagnetic [M(C₂O₄)₃]^n– complex (M = Cr^III, n = 3 or M = Co^II, n =4) inside. The incorporation of the chiral-at-metal complex insidethe cage alters the chiroptical properties compared with the Co^II₅L₆ framework encaging carbonate ions.Furthermore, the cage framework and the encapsulated chiral-at-metalcomplex exhibit significant magnetic interactions. The variation ofthe metal types in the encapsulated chiral-at-metal complex or thecage frameworks can modulate the magnetic interactions, from antiferromagnetismto ferromagnetism with different exchange strengths. This study providesa new option for the design of cage materials combining chiralityand magnetism.

Dinuclearmetal synergistic catalysis (DMSC) has beenwell establishedas an effective strategy for enhancing catalytic efficiency in variousfields. However, the design of catalysts for the DMSC-enabled hydroborationof terminal alkynes has been rarely reported. Herein, we report thesynthesis of a novel copper-based hydrogen-bonded organic framework(HOF), denoted as Cu-PzDC. Benefiting from its planar dinuclear Cuunits, Cu-PzDC exhibits exceptionally high catalytic efficiency towardthe hydroboration of terminal alkynes, achieving complete conversionwithin merely 30 min at room temperature without the need of inertatmosphere. This catalytic system affords the synthetically valuableβ-(E)-vinylboronates with 99% selectivity anddemonstrates a broad substrate compatibility covering 29 examples.DFT calculations reveal the synergistic effect between two adjacentCu sites, which enables the simultaneous activation of boryl speciesand phenylacetylene and brings them into close proximity.

Biomineralizationdescribes how living organisms orchestrate thesynthesis of functional inorganic materials for structural protectionor mechanical support. Mineralization under biological regulationoften involves amorphous mineral phases, such as amorphous calciumcarbonate or amorphous calcium phosphate, that lack long-range orderand transform into stable crystals over time. Unlike calcium-bearingbiominerals, little work has been dedicated toward understanding thebiomineralization of earth alkaline sulfates. To our knowledge, thisstudy is the first to unambiguously detect a transient amorphous strontiumsulfate (ASS) phase using time-resolved X-ray diffraction and TransmissionElectron Microscopy (TEM) under cryogenic conditions. Specifically,the incorporation of the negatively charged polysaccharide heparinwas found to mediate bioinspired crystallization pathways based onfundamental inorganic–organic interactions, guiding an amorphous-to-crystallinetransformation of the strontium sulfate (SrSO₄) mineral.The process yielded unusual ellipsoidal SrSO₄ microcrystalsthat partially underwent particle–particle fusion. Nanofocusedsynchrotron wide-angle X-ray scattering and high-resolution TEM revealedmesocrystalline order from imperfect attachment of ASS nanoclusters,with crystal lattice planes exhibiting gradual tilts in orientation.The nonlinear optical properties of SrSO₄ crystals openintriguing avenues for solid-state optical devices used for IR-to-visiblelight conversion.

We report a comprehensive structural characterizationof La₂PrNi₂O₇, a bilayer Ruddlesden–Poppernickelate that has been described to exhibit high-temperature superconductivityunder hydrostatic pressure. Synchrotron X-ray diffraction (SXRD) dataand high-resolution neutron powder diffraction (NPD) data, collectedat ambient pressure, together with NPD data recorded under pressuresup to 8.42 GPa in a Paris–Edinburgh cell, have been analyzedby the Rietveld method in the orthorhombic Amam spacegroup (No. 63). This work aims at providing precise bulk structuralbenchmarks─site-selective cation distribution, oxygen stoichiometry,and the pressure evolution of the Ni–O–Ni bond geometry─thatare essential inputs for theoretical models. High-resolution NPD,which offers a strong La/Pr scattering-length contrast, yields refinedLa/Pr occupancies that suggest a slight preference of Pr for the outerrock-salt site (La2/Pr2), although the deviation from a random distributiondoes not exceed three standard deviations and is therefore not statisticallyconclusive. NPD also assesses the full oxygen stoichiometry of thespecimen under study. Under applied pressure up to 8.42 GPa (belowthe superconducting critical pressure P_c ≈ 11 GPa), the orthorhombic structure is retained with asystematic compression of all lattice parameters, a reduction of theunit-cell volume of ∼4.9%, and a progressive straighteningof the out-of-plane Ni–O–Ni bond angle. No structuralphase transition to the tetragonal I4/mmm symmetry is observed in the pressure range studied, consistent withthe superconducting onset occurring above P_c ≈ 11 GPa. Cooling to 5 K at 8.42 GPa produces no measurableadditional structural change, indicating that precursor distortionsto the superconducting state are subtle.

Open d-shell transition-metal oxides are widely studiedas photoactivematerials for solar-energy conversion but typically exhibit low yieldsof mobile photocarriers. This inefficiency has been linked to ligand-field(LF) states that induce ultrafast relaxation, although their impactacross open d-shell oxides remains poorly understood. Here, epitaxialilmenite-type MTiO₃ (M = Ni, Co, Mn) thin films were stabilizedby pulsed laser deposition. In this isostructural series, the M²⁺ cation tunes the d-electron configuration and the energeticseparation and spectral overlap of LF and charge-transfer excitations.Combined optical and time-resolved microwave conductivity measurements,benchmarked against rutile TiO₂ as a d⁰ reference,together with photoelectrochemical measurements of the ilmenites,reveal reduced yield-mobility products compared to TiO₂. NiTiO₃ and CoTiO₃ show measurable photoconductivityonly under UV charge-transfer excitation, whereas MnTiO₃, dominated by a dense LF manifold, exhibits a negligible response.These results indicate that mobile charge-carrier generation contributingto photoelectrochemical activity originates from UV charge-transferexcitations, likely dominated by O^2– → Ti⁴⁺ ligand-to-metal charge-transfer (LMCT) excitation into Ti3d-derived states, while LF states primarily act as relaxation pathwaysthat do not yield mobile carriers on nanosecond time scales. Thesefindings decouple the roles of distinct optical excitations in governingphotocarrier localization in open d-shell oxides.

Natural gas, as a clean energy source, requires the eliminationof co-occurring impurities such as C₂H₆ andC₃H₈ to enhance its energy utilization efficiency.Herein, by using a Zr-based MOF as a platform, we fabricated an isostructuralpair, NU-1400(−H) and fluorine-functionalized NU-1400(−F), through rational ligand fluorination,and systematically investigated their adsorption and separation performancestoward CH₄, C₂H₆ and C₃H₈. This isostructural pair allows the effect of fluorinefunctionalization on the pore microenvironment and adsorption affinityto be directly evaluated. Single-component adsorption isotherms revealthat fluorine functionalization significantly improves the uptakecapacities of C₂H₆ and C₃H₈ (from 25.4/28.8 to 34.1/38.9 cm³ g^–1), while causing only marginal changes in CH₄ adsorption.Isosteric heat of adsorption (Q_st) analysisconfirms that NU-1400(−F) exhibits weakened affinityfor CH₄ (19.2 kJ mol^–1) and remarkablyenhanced interaction with C₃H₈ (47.3 kJ mol^–1). Benefiting from such optimized differences in adsorptionaffinity, NU-1400(−F) achieves excellent IASTselectivity of 516 for C₃H₈/CH₄ and21 for C₂H₆/CH₄, which are far higherthan those of pristine NU-1400(−H) (145 and 18).Dynamic breakthrough experiments and cyclic regeneration tests furthervalidate its reliable separation capability and outstanding recyclability.The rational fluorine functionalization effectively tailors the poremicroenvironment for selective heavy-hydrocarbon adsorption, making NU-1400(−F) a promising adsorbent for one-step methanepurification from natural gas. This work thus highlights a practicalpore-microenvironment engineering strategy via ligand fluorinationfor efficient light hydrocarbon/CH₄ separation.